CN115124350B - Preparation process of ceramic composite material applied to high-temperature environment - Google Patents
Preparation process of ceramic composite material applied to high-temperature environment Download PDFInfo
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- CN115124350B CN115124350B CN202210728537.4A CN202210728537A CN115124350B CN 115124350 B CN115124350 B CN 115124350B CN 202210728537 A CN202210728537 A CN 202210728537A CN 115124350 B CN115124350 B CN 115124350B
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 82
- 229910007948 ZrB2 Inorganic materials 0.000 claims abstract description 47
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims abstract description 47
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002490 spark plasma sintering Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 8
- 238000000280 densification Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
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Abstract
The invention relates to ZrB 2 The technical field of preparation of base high-temperature ceramics, and discloses a preparation process of a ceramic composite material applied to a high-temperature environment, which comprises the following steps: zirconium diboride ZrB with micron particle size 2 Generating chromium-copper composite cluster particles with nanometer particle size on the particles, calcining the particles under vacuum and adopting hydrogen for reduction in the calcining process to obtain zirconium diboride ZrB 2 Chromium copper cluster particle coated composite powder, and zirconium diboride ZrB applied to high temperature environment is prepared by adopting a discharge plasma sintering method 2 Chromium copper cluster particle coated ceramic composite material with fracture toughness up to 5.84-6.27 MPa-m 1/2 And achieve the reduction of zirconium diboride ZrB 2 The sintering temperature of the particles, the densification promotion and the excellent high-temperature oxidation resistance.
Description
Technical Field
The invention relates to ZrB 2 The technical field of preparation of base high-temperature ceramics, in particular to a preparation process of a ceramic composite material applied to a high-temperature environment.
Background
Due to ZrB 2 The intermediate extremely strong covalent bond structure and low atomic diffusivity, and no liquid phase and gas phase transmission path exists in the preparation process, so that the single-phase compact ZrB can be obtained by sintering under the conditions of extremely high temperature, long-time heat preservation and pressure application 2 A bulk material. Except ZrB 2 In addition to the intrinsic factors of (a), the reduction of the particle size of the powder, the improvement of the purity of the powder and the reduction of the oxygen content promote ZrB 2 Densification of ceramic materials. In addition, in ZrB 2 The sintering auxiliary agent is added, so that not only can the sintering densification of the material be promoted, but also the ZrB can be promoted and prepared 2 Mechanical and oxidation resistance of the base ultra-high temperature ceramic.
At present, zrB 2 The sintering aids added in the process can be divided into the following categories: 1) Metal powders, such as Fe, ni, cr, etc., melt to form liquid phase filling the gaps between ceramic powders during high temperature sintering, thereby promoting densification of the material; 2) Nonmetallic powders, such as C, B, etc., can be prepared by eliminating ZrB 2 Impurities on the surface of the powder promote sintering densification of the material; 3) Ceramic powders, e.g. B 4 C、Si 3 N 4 [, alN, zrN, hfN, siC, etc., such sinteringThe densification mechanism of the auxiliary agent mainly comprises: with ZrB 2 The surface impurities react to purify grain boundaries, generate low-melting-point products, soften and deform themselves, and the like.
Disclosure of Invention
(one) solving the technical problems
For ZrB 2 The invention provides a preparation process of a ceramic composite material applied to a high-temperature environment, which has the defects of poor sintering compactness, low plastic toughness and easiness in high-temperature oxidation.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation process of a ceramic composite material applied to a high-temperature environment comprises the following steps:
step S1, zirconium diboride ZrB with micron particle size 2 Generating chromium-copper composite cluster particles with nanometer particle size on the particles, calcining the particles under vacuum and adopting hydrogen for reduction in the calcining process to obtain zirconium diboride ZrB 2 -chromium copper cluster particle coated composite powder;
step S2, using zirconium diboride ZrB 2 Chromium-copper cluster particle coated composite powder as raw material and adopting discharge plasma sintering method to prepare zirconium diboride ZrB applicable to high temperature environment 2 Chromium copper cluster particle coated ceramic composite.
Preferably, the step S1, zirconium diboride ZrB 2 The particle diameter of the particles is more than or equal to 1um and less than or equal to 15um; the particle size of the chromium-copper composite cluster particles is more than or equal to 10nm and less than or equal to 50nm.
Preferably, in the step S1, zirconium diboride ZrB with the micron particle size 2 Generating chromium-copper composite cluster particles with nanometer particle size on the particles, calcining the particles in vacuum at 350-380 ℃ for 1-2h, and reducing the particles with hydrogen at 620-680 ℃ for 1-3h to obtain zirconium diboride ZrB 2 Chromium copper cluster particle coated composite powder.
Preferably, in the step S2, the parameters of the spark plasma sintering process are as follows: the initial pressure is 8-15MPa, the pressure is increased to 18-20MPa under vacuum, and the temperature is kept for 7-15min under vacuum condition of 1680-1750 ℃ and 18-20 MPa.
(III) beneficial technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
zirconium diboride ZrB with particle size not less than 1um and not more than 15um 2 Chromium-copper composite cluster particles with the particle diameter of more than or equal to 10nm and less than or equal to 50nm are generated on the particles, calcined under vacuum and reduced by adopting hydrogen to obtain zirconium diboride ZrB 2 Chromium copper cluster particle coated composite powder prepared from zirconium diboride ZrB 2 The particles are inner cores, and chromium copper cluster particles are outer shells;
with zirconium diboride ZrB 2 Chromium-copper cluster particle coated composite powder as raw material and adopting discharge plasma sintering method to prepare zirconium diboride ZrB applicable to high temperature environment 2 Chromium copper cluster particle coated ceramic composite material with fracture toughness up to 5.84-6.27 MPa-m 1/2 ；
In zirconium diboride ZrB 2 In the chromium-copper cluster particle core-shell coated ceramic composite material, the chromium-copper cluster particles (chromium melting point 1907 ℃ and copper 1083 ℃) have better plastic toughness and can keep higher strength at normal temperature, and copper is melted into liquid state at high temperature higher than copper melting temperature 1083 ℃ to show plastic toughness and can enter zirconium diboride ZrB 2 The hollow of the particles helps mass transfer, and plays a role in reducing zirconium diboride ZrB 2 The sintering temperature of the particles and the effect of promoting densification;
and when oxygen diffuses to the surface of the material, cr can be formed 2 O 3 Passivation protection film for blocking oxygen ions to zirconium diboride ZrB 2 Particle diffusion of zirconium diboride ZrB 2 The particles play a role in protecting, so that the particles have excellent high-temperature oxidation resistance.
Detailed Description
Example 1:
zirconium diboride ZrB 2 Preparation of chromium copper cluster particle coated composite powder:
will 3.2g CrCl 3 Dispersing in 100mL distilled water, and dripping 100mL solution containing 4.5g by a constant pressure funnel at a rate of 30 drops/min under stirringDistilled aqueous solution of sodium borohydride, 1g of CuSO was added to the above solution 4 10g of potassium sodium tartrate, 10g of ethylenediamine tetraacetic acid and 5mg of 2, 2-bipyridine, adjusting the pH to 10, heating to 60 ℃ and heating in a constant-temperature water bath, adding 5g of zirconium diboride ZrB2 particles with an average particle size of 1-2um and 5mg of PdCl into the solution under stirring 2 Refluxing at 60deg.C for 6 hr, and collecting zirconium diboride ZrB with average particle diameter of 1-2um 2 Chromium-copper composite cluster particles with the particle diameter of more than or equal to 10nm and less than or equal to 50nm are generated on the particles, nitrogen is always introduced in the whole process, and the zirconium diboride ZrB is obtained after filtering, washing, vacuum drying, vacuum calcining for 1h at 360 ℃ and hydrogen reduction for 2h at 650 DEG C 2 -chromium copper cluster particle coated composite powder;
with zirconium diboride ZrB 2 The chromium copper cluster particle coated composite powder is used as a raw material, a discharge plasma sintering method is adopted, three-high graphite is used as a discharge plasma sintering die, and cylindrical zirconium diboride ZrB with the diameter of 2cm and the length of 7cm is sintered 2 The ceramic composite material coated by chromium copper cluster particles has the following technological parameters of spark plasma sintering: the initial pressure is 10MPa, the pressure is increased to 20MPa under vacuum, the temperature is increased to 1600 ℃ at the speed of 80 ℃/min, then the temperature is increased to 1720 ℃ at the speed of 50 ℃/min, the temperature is kept for 10min under the vacuum condition of 1720 ℃ and 20MPa, and the temperature is reduced.
Example 2:
zirconium diboride ZrB 2 Preparation of chromium copper cluster particle coated composite powder:
will 2.5g CrCl 3 Dispersing in 100mL distilled water, dropping 100mL distilled water solution containing 3g sodium borohydride dissolved therein at a rate of 30 drops/min from a constant pressure funnel under stirring, and adding 0.8g CuSO to the above solution 4 8g of potassium sodium tartrate, 8g of ethylenediamine tetraacetic acid and 5mg of 2, 2-bipyridine, adjusting the pH to 10, heating to 50 ℃ and heating in a constant-temperature water bath, adding 5g of zirconium diboride ZrB with an average particle size of 3-5um into the solution under stirring 2 Particle and 5mgPdCl 2 Refluxing at 50deg.C for 8 hr, and collecting zirconium diboride ZrB with average particle diameter of 3-5um 2 Chromium-copper composite cluster particles with the particle diameter of more than or equal to 10nm and less than or equal to 50nm are generated on the particles, and are always introduced in the whole processFiltering, washing and vacuum drying nitrogen, then calcining for 1h at 350 ℃ in vacuum, and reducing for 1h at 620 ℃ by adopting hydrogen to obtain zirconium diboride ZrB 2 -chromium copper cluster particle coated composite powder;
with zirconium diboride ZrB 2 After compression molding, adopting a discharge plasma sintering method, taking three-high graphite as a discharge plasma sintering die, and sintering to obtain cylindrical zirconium diboride ZrB with the diameter of 2cm and the length of 7cm 2 The ceramic composite material coated by chromium copper cluster particles has the following technological parameters of spark plasma sintering: the initial pressure is 8MPa, the pressure is increased to 20MPa under vacuum, the temperature is increased to 1560 ℃ at the speed of 80 ℃/min, then to 1680 ℃ at the speed of 50 ℃/min, then the temperature is kept for 15min under the vacuum condition of 1680 ℃ and 20MPa, and then the temperature is reduced.
Example 3:
zirconium diboride ZrB 2 Preparation of chromium copper cluster particle coated composite powder:
4g of CrCl 3 Dispersing in 100mL distilled water, dropping 100mL distilled water solution containing 8g sodium borohydride dissolved therein at a rate of 30 drops/min from a constant pressure funnel under stirring, and adding 1.5g CuSO to the above solution 4 15g of potassium sodium tartrate, 15g of ethylenediamine tetraacetic acid and 10mg of 2, 2-bipyridine, adjusting the pH to 10, heating to 80 ℃ and heating in a constant-temperature water bath, adding 5g of zirconium diboride ZrB with an average particle size of 15um into the solution under stirring 2 Particle and 10mgPdCl 2 Refluxing at 80deg.C for 4 hr, and collecting zirconium diboride ZrB with average particle diameter of 15um 2 Chromium-copper composite cluster particles with the particle diameter of more than or equal to 10nm and less than or equal to 50nm are generated on the particles, nitrogen is always introduced in the whole process, and the zirconium diboride ZrB is obtained after filtering, washing, vacuum drying, vacuum calcining for 2 hours at 380 ℃ and hydrogen reduction for 3 hours at 680 DEG C 2 -chromium copper cluster particle coated composite powder;
with zirconium diboride ZrB 2 After compression molding, the chromium copper cluster particle coated composite powder is sintered into a composite powder with a diameter of 2cm and a length of 7cm by adopting a discharge plasma sintering method and adopting three-high graphite as a discharge plasma sintering dieIs a cylindrical zirconium diboride ZrB 2 The ceramic composite material coated by chromium copper cluster particles has the following technological parameters of spark plasma sintering: the initial pressure is 15MPa, the pressure is increased to 18MPa under vacuum, the temperature is increased to 1650 ℃ at the speed of 80 ℃/min, then to 1750 ℃ at the speed of 50 ℃/min, then the temperature is kept for 7min under the vacuum condition of 1750 ℃ and 18MPa, and then the temperature is reduced.
Comparative example 1:
zirconium diboride ZrB with average grain size of 1-2um 2 After the particles are used as raw materials and pressed and formed, a discharge plasma sintering method is adopted, three-high graphite is used as a discharge plasma sintering die, and cylindrical zirconium diboride ZrB with the diameter of 2cm and the length of 7cm is sintered 2 The ceramic material has the following technological parameters of spark plasma sintering: the initial pressure is 10MPa, the pressure is increased to 20MPa under vacuum, the temperature is increased to 1600 ℃ at the speed of 80 ℃/min, then the temperature is increased to 1720 ℃ at the speed of 50 ℃/min, the temperature is kept for 10min under the vacuum condition of 1720 ℃ and 20MPa, and the temperature is reduced.
Performance test:
1. according to GB/T6569-2006, a three-point bending method is adopted on a WDW-5 microcomputer control electronic universal testing machine to measure bending strength;
2. according to GB/T23806-2009, fracture toughness testing is carried out on an electronic universal testing machine;
3. testing the Vickers hardness by using a 432SVD microhardness tester;
the results of the above tests are shown in Table 1 below;
TABLE 1
Claims (2)
1. The preparation process of the ceramic composite material applied to the high-temperature environment is characterized by comprising the following steps of:
step S1, wherein the grain diameter of zirconium diboride ZrB is more than or equal to 1um and less than or equal to 15um 2 Chromium-copper composite cluster particles with the particle diameter of more than or equal to 10nm and less than or equal to 50nm are generated on the particles, calcined under vacuum and reduced by adopting hydrogen to obtain zirconium diboride ZrB 2 Chromium copper cluster particle coated composite powder prepared from zirconium diboride ZrB 2 The particles are inner cores, and chromium copper cluster particles are outer shells;
step S2, using zirconium diboride ZrB 2 The chromium-copper cluster particle coated composite powder is used as a raw material, and a discharge plasma sintering method is adopted, wherein the discharge plasma sintering process parameters are as follows: firstly, increasing the pressure to 18-20MPa under vacuum, then heating to 1680-1750 ℃, preserving the heat for 7-15min under the vacuum condition of 1680-1750 ℃ and 18-20MPa, and finally cooling to prepare the zirconium diboride ZrB applied to the high temperature environment 2 Chromium copper cluster particle coated ceramic composite.
2. The process for preparing a ceramic composite material applied to a high-temperature environment according to claim 1, wherein the process parameters of the spark plasma sintering in step S2 are as follows: the initial pressure is 8-15MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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